Condensation products and methods of preparing and using the same



Patented Sept. 18, 1945 OFFICE;

CONDENSATION PRODUCTS AND METHODS OF PREPARING AND USING THE SAME Eugene Lieber, Staten Island, N. Y., assignor. to

pment Company, a corpo- Standard Oil Develo ration of Delaware No Drawing. Application November Serial No. 366,707

7 Claims. (Cl. 260-592) This invention relates to a novel type of chemical condensation products and to methods of preparing such products and using them for various purposes more particularly as pour depressors .in waxy lubricating oils.

Broadly, this invention comprises the production of a novel type of condensation product by reacting an aliphatic aromatic ketone' with a resinifying agent, especially in order to produce an oil-soluble condensation product.

The aliphatic aromatic ketone to be used is preferably .one having the general formula RCOAr, in which R represents an aliphatic group and Ar is an aromatic group. The group R is preferably an aliphatic hydrocarbon group and preferably contains more than 10 carbon atoms.

produce high molecular weight condensation products having wax-modifying properties. This interlinking agent is preferably a carbonyl-group- 'containing organic compound and is preferably selected from the class consisting of aldehydes and ketones of a sufficiently low molecular weight to effect the desired interlinking action. Ex-

Also, although some slightly unsaturated aliphatic groups can be used, such as the group attached to the carbonyl radical in the oleyl group obtained from oleic .acid, it-is preferred to use saturated (i. e., alkyl) groups, such as the heptadecyl group, attached to the carbonyl radical in the stearyl group obtained from stearic acid, or the corresponding cetyl and octadecyl groups as well as mixed groups, such as those obtained fromparaffin wax oxidation acids. The groupAr may represent benzene, naphthalene, anthracene, phenanthrene, diphenyl, toluene, xylene, phenoLaIphaor beta-naphthol, cresol, aniline, alpha-naphthylamine, tertiary-amyl phenol, etc. sired, various other derivatives of such ketones may be used. The aliphatic group R may also contain various substituents, e. g., hydroxy, methyl, ethyl, chloro, amino, and the like.

Although the preparation of such ketones does 35 not constitute part of the present invention, it may be explained that they may be suitably prepared by condensing fatty acid chlorides, e.- g., stearyl chloride, with a suitable aromatic compound, e.,g., benzene, naphthalene, or mixed aromatic compounds, such as those obtained from coal-tar fractions; this condensation is usually carried out by means of a Friedel-Craft catalyst.

Also, if deamples of materials of this class include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, acetone, methyl ethyl acetone, ispropyl ketone, etc. These compounds should in general have no more than 10 carbon atoms and preferably no more than 4 carbon atoms. They may be represented by the general formula R'COX. where X is hydrogen orv R (either the same or different) and B. may also be hydrogen (formaldehyde) The primary chemical reaction involved in the present invention is probably expressed by the following chemical equation: 2RCOAr+R'COX= This reaction is probably accompanied or followed by other substantially similar reactions, in which the product of the first reaction is interlinked with additional molecules of the aliphatic aromatic ketone with the resultant formation of higher molecular condensation products which may be considered to have a linear-chain type structure. One graphic representation of such a product is as follows:

Thus the high molecular weight condensation products may be considered to have the general formula RCOAr [(R')C(X)AICQR]1|, where n is a subscript indicating the number of monomeric During the preparation of such ketones, some substances having what may be termed a compound-ketone structure such as those having the general formula RCOArCOR, are sometimes formed and may be used along with the main ketone product.

. The other reactant to be usedaccording to this invention is a resinifying or interlinking agent which is instrumental in coupling together successive molecules of the aliphatic aromatic ketone until chains of sufficient length are built up to u unitscondensed together or, mother words, the degree of condensation, and the other letters have the meanings indicated above.

To effect the condensation. it is preferred to use a condensation catalyst, preferably a dehydrating agent, such as sulfuric acid, zinc chloride, boron trifluoride, stannic and/or stannous chloride, zinc oxide, phosphoric acid, phosphorus pentoxide, ferric chloride, .etc. If sulfuricacid is used, it is often desirable, although not necessary, to use some glacial acetic acid as a solvent or promoter;

it acts as a dehydrating solvent and is not a catalyst for the reaction by itself;

cases it is a viscous oil and The proportions in which the reactants should be used are preferably to 5, or preferably 1 to 3, mols of interlinking agent to one mol of the aliphatic aromatic ketone. The amount of conassesses as a Pennsylvania type lubricating oil having a relatively high pour point, the resultant blend will have a substantially lower pour point; in other words, this wax modifier is an effective pour densing agent may vary to a large extent,'de- 5 depressor for waxy oils. A small amount of this pending partly upon the nature and amount of wax modifier is also useful as a dewaxing aid for reactants as well as primarily upon the temperremoving wax from mineral lubricating oils of ature and the desired reaction time, but usually undesirably high wax content. In similarly it should be about to 5 mols to one mol of the small amounts, this wax modifier may also be inhigh molecular weight aliphatic aromatic kel corporated into paraflin wax or compositions tone. If glacial acetic acid is used, the amount containing the same to be used for various purshould be between the approximate limits of 50% poses such as for coating or impregnating paper, and 500% by weight based on the aliphatic aroetc. or for making various molded products. matic ketone. For the sake of illustration but without de- In carrying out the invention, the reaction 15 siring to limit the invention to the particular temperature should be maintained between the materials used, some experimental data are given. approximate limits of 100 and 300 F., preferably In carrying out these tests the general procedure 150 to 250 F., and the reaction time, which obvidescribed hereinbefore was-used- In making the ously varies inversely with the temperature pour-point test a small amount of the condenshould be about /2 to 10 hours, or usually about 0 sation product was dissolved in a mineral lubril to hours. cating 011 base stock having a pour point of +30 When the reaction has been completed it is F., the pour point of the resulting blends being generally desirable to cool the reaction mixture shown in the table.

Table Condensation product Test Mixed ketono Aldehyde Catalyst points a R) No Temp. Time oiblends made Yield withadd1t1onoi- Name Gms. Name Gms. Name Gms. 1.0% 2.0% 5.0%

F. Hours 1 Stearyl benzen 2 .....d0 105 Form-.-..- 27 msoum- 100 150 a 3 do 106 d.o 27 do- 100 150 1 4 do 105 m 9 25 160 1 5 (in 105 tn 9 50 150 1 6 do 105 m 9 100 150 1 7 -...do 105 .-...c.o.- 9 do 100 200 1 8 Stearyl nh 9 d0 I in) Form-"h- 9 H1504-.- 100 200 1 10 do 250 .do....- ZnCh..-.. 175 2 11 Wax-naphthalene 12 do 12o Bonn-u-.- 14 Bison--- 200 175 1% 13 .....do 12o Butyr-.. 24 do. 100 150 1 14 240 do 48 ZnCh- 48 175 2 15 Wax-benzene 10 do 105 Form-. 14 11,500... 200 175 1% 17 an 105 Butyr-... 24 do 100 150 1 is ..do 210 ....do.. it ZnCla".-- 42 175 a 19 Stearyl phenol 20 .do ss Form--. 1 15118041... 77 150 1 21 do 216 ...do..... is ZnC 44 175 a I Nome-Test Nos 1, 8, 11, 15 and 19 are control experiments. Formmeans formaldehyde, which is used in the form of trioxy methylene.

oh 0. 1 200 cc. of glacial mt acid were also used. 1 Made from wax acids obtained by about equal to that oi stesrio acid.

and dilute it, both steps being accomplished by adding a substantial volume of water. Then the reaction mixture is extracted with a refined kerosene, and afterwards settled; the kerosene layer is washed with water until tree or acid and finally distilled under vacuum or with fire and steam to about 600 F., in order to remove the solvent and low boiling products.

The distillation residue is the desired high oxidation oi parsilin wax. The acids used in these experiments had an average molecular weight -15 F., thus indicating that very potent pour molecularweight condensation product. It is soluble in mineral lubricating oils and is substantially non-volatile at about 600 F. In most has a color usually ranging from red to brown, although sometimes depressors can be made from raw materials which have only weak, if any, pour-depressing effects.

It is not intended that this invention be limited to any of the specific examples which were given merely for the sake of illustration nor to anytheory as to the mechanism of the operation of the invention but only by the appended claims 1 in which it is intended to claim all novelty inherent in the invention as broadly as the prior art permits.

oil such 7 I claim:

s. 'lheprocessaccordingtoclaimecarried out and glacial acetic 1. The process which comprises reacting an allryl aryl ketone with a low molecular weight carbonyl group-containing interlinking agent compound selected from the group consisting of aldehydes and ketones containing less than 10 car- -bon atoms, with. the assistance ot a dehydrating catalyst at a temperature of about 100to 300 F. and subjecting the reaction mixture to fire and ste;a r n distillation up to about 600 F. to obtain the desired condensation as distillation residue.

2. The process which comprises reacting one mol of alkyl aryl ketone with 55 to mols oi low molecular weight aldehyd having less than carbon atoms, in the presence of a dehydratingiecting the reaction mixture to fire and steam distillation up to about 600 F. to obtain the desired high molecular weight oil-soluble condensation product as distillation residue.

in the presence of sulfuric acid acid.

6. The process which comprises reacting a ketone having the seneral formula RCOAr, where R is an aliphatic group having more than 10 carbon atoms and Ar is an aromatic group, with a low molecular weight aliphatic interlinking agent containing a carbonyl group and selected from the group consisting oi aldehydes and hetones containing less than -10 carbon atoms, and

subjecting the reaction mixture to distillation up to 000 1". under reduwd pressure to obtain the desired condensation product as distillation nesidue.

7. A high molecular weight oil-soluble condensation product which has been obtained by reacting an alkyl aryl .ketone with a low molecular weight carbonyl group-containing interlinking agent compound selected from the group consisting oi aldehydes and ketones containing less than 10 carbon atoms with the assistance of a dehydratingcatalyst at a temperature oi about to 300 It, subjecting the reaction mixture to fire and steam distillation up to about 600 l". to obtain the desired condensation product as distillation residue and recovering said distillation residue.

. EUGENE 1mm. 

